CN102543478A - Method for improving specific volume of low voltage aluminum anode foil - Google Patents
Method for improving specific volume of low voltage aluminum anode foil Download PDFInfo
- Publication number
- CN102543478A CN102543478A CN201210010926XA CN201210010926A CN102543478A CN 102543478 A CN102543478 A CN 102543478A CN 201210010926X A CN201210010926X A CN 201210010926XA CN 201210010926 A CN201210010926 A CN 201210010926A CN 102543478 A CN102543478 A CN 102543478A
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- CN
- China
- Prior art keywords
- foil
- aluminium foil
- aluminum
- specific volume
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 29
- 239000011888 foil Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000005030 aluminium foil Substances 0.000 claims description 60
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001741 Ammonium adipate Substances 0.000 claims description 22
- 235000019293 ammonium adipate Nutrition 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002203 pretreatment Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 210000004940 nucleus Anatomy 0.000 abstract 3
- 239000007788 liquid Substances 0.000 abstract 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Abstract
The invention provides a method for improving specific volume of a low voltage aluminum anode foil, being capable of reducing chloride ion content, reducing leakage current density and improving the specific volume of the aluminum anode foil. The method provided by the invention is mainly characterized in that: chloride ion in the aluminum anode foil is separated out more rapidly by utilizing electrochemical treatment in the initial period of formation and uniform and dense aluminum oxide crystal nucleuses are formed in an aluminum foil; concentration, temperature and exchange traffic of forming liquid as well as size of on load voltage and magnitude of current are adjusted, and corrosion reaction between residual chloride ion in the aluminum foil and the aluminum foil is reduced, thus the residual chloride ion is diffused into the forming liquid; meanwhile, plenty of aluminum oxide crystal nucleuses are formed in the aluminum foil, the crystal nucleuses grow continuously in a subsequent anode oxidation process, and content of crystal alumina in a dielectric layer is improved, thus the specific volume of the aluminum anode foil is improved. Compared with untreated aluminum anode foil, the specific volume of the aluminum foil can be improved by 3-20%, and leakage current density is reduced by 40-60%. The method provided by the invention can be directly applied to the current industrial large-scale production.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to a kind of method that improves low-voltage aluminum electrolytic capacitor with the anode aluminium foil specific volume.
Background technology
Aluminium oxide is the working media of aluminium electrolytic capacitor, is the core of aluminium electrolytic capacitor, and many performances of its film quality decision aluminium electrolytic capacitor are like leakage current, loss, life-span, capacitance etc.Therefore; The researcher studies the formation technology of aluminium oxide from theory and practice all the time; Make that aluminium oxide rete quality obtains to improve constantly; Simultaneously, the formation to aluminium oxide also obtains certain common recognition: the remaining impurities chloride ion makes the performance of the pellumina of anodic oxidation formation be difficult to guarantee that the crystal formation pellumina then helps improving the aluminium electrolytic capacitor performance in the aluminium foil.
In recent years, along with the extensive use of aluminium electrolytic capacitor at emerging fields such as portable electronics, industrial frequency conversion, new forms of energy, electric automobile, high ferro traffic, the increasingly high requirement of performance proposition to aluminium electrolytic capacitor requires outstanding especially with high specific volume.Therefore, the various countries scientific research personnel is carrying out unremitting effort aspect the raising aluminium foil specific volume, and one of them main research direction is to improve the aluminium foil effective ratio area through electrochemical corrosion to improve the aluminium foil specific volume, has obtained considerable progress.
But along with the requirement of antianode aluminium foil specific capacity is increasingly high, cause the thickness of used aluminium foil more and more thicker, extent of corrosion is increasingly high; The corrosion hole becomes more and more darker, and shape becomes increasingly complex, and it is more and more tiny that the hole end also becomes; Make the corrosive agent chloride ion in the corrosion hole be difficult to clean thoroughly; Inner residual a large amount of chloride ion increases aluminium foil anodic oxidation difficulty subsequently, causes the reduction of properties of oxide-film.
At present; After generally following the aluminium foil corrosion operation closely to the matting of residual chlorine ion; The method that adopts is also mostly to be nitrate method, few removal of considering the residual chlorine ion in the forming process of aluminium foil, and this has reduced the anode aluminium foil specific capacity to a great extent, has increased its leakage current density.
Summary of the invention
The purpose of this invention is to provide and a kind ofly both be fit to the extensive interlock of industry and produce, can reduce the method for raising low voltage anode aluminum foil specific volume of the leakage current of anode oxide film again.
For achieving the above object, the technical scheme that the present invention adopts is:
1) electrochemical pre-treatment: it is 15～20% ammonium adipate solution that corrosive aluminum foil is placed 40～60 ℃, mass concentration, loads 2～5V, 10～300mA/cm
2Voltage and current carry out anodic oxidation, load time 40～80S improves 1～3 times of the switching traffic of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 5～10% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 80～90 ℃, mass concentration, loads 10-100V, 200～1000mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 500～600 ℃ of following heat treatment 2～5min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
The present invention adopts the method for electrochemical pre-treatment; At first corrosive aluminum foil is carried out anodic oxidation under the condition of the switching traffic of lower temperature, low low pressure, small electric current density, big ammonium adipate solution; Make the chloride ion in the aluminium foil accelerate to separate out and in aluminium foil, form the aluminium oxide nucleus of even compact; Subsequently, through temperature, formation electric current and the heat treatment temperature that improves electrolyte, promote the preferred growth of nucleus; Improve the content of crystalline solid in the alumina medium film, realize the raising of anodic oxidation aluminium foil specific volume.With untreated formation aluminium foil (21Vf aluminium foil specific capacity 70 μ F/cm
2, leakage current density 25mA/cm
2) compare, the present invention can improve aluminium foil specific volume 3～20%, reduce leakage current density 40～60% (21Vf aluminium foil specific capacity 72-84 μ F/cm
2, leakage current density 10-15mA/cm
2).
Embodiment
Embodiment 1:
1) electrochemical pre-treatment: it is 20% ammonium adipate solution that corrosive aluminum foil is placed 50 ℃, mass concentration, loads 2V, 10mA/cm
2Voltage and current carry out anodic oxidation, load time 80S improves 2 times of the switching traffics of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 5% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 90 ℃, mass concentration, loads 10V, 1000mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 550 ℃ of following heat treatment 3.5min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Embodiment 2:
1) electrochemical pre-treatment: it is 15% ammonium adipate solution that corrosive aluminum foil is placed 40 ℃, mass concentration, loads 5V, 50mA/cm
2Voltage and current carry out anodic oxidation, load time 40S improves 3 times of the switching traffics of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 10% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 80 ℃, mass concentration, loads 50V, 600mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 600 ℃ of following heat treatments 3.5,2,4,3,5min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Embodiment 3:
1) electrochemical pre-treatment: it is 18% ammonium adipate solution that corrosive aluminum foil is placed 60 ℃, mass concentration, loads 3V, 200mA/cm
2Voltage and current carry out anodic oxidation, load time 60S improves 1 times of the switching traffic of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 8% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 85 ℃, mass concentration, loads 30V, 300mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 520 ℃ of following heat treatment 4min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Embodiment 4:
1) electrochemical pre-treatment: it is 16% ammonium adipate solution that corrosive aluminum foil is placed 55 ℃, mass concentration, loads 4V, 100mA/cm
2Voltage and current carry out anodic oxidation, load time 50S improves 2 times of the switching traffics of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 6% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 82 ℃, mass concentration, loads 80V, 800mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 580 ℃ of following heat treatment 3min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Embodiment 5:
1) electrochemical pre-treatment: it is 19% ammonium adipate solution that corrosive aluminum foil is placed 45 ℃, mass concentration, loads 3V, 300mA/cm
2Voltage and current carry out anodic oxidation, load time 70S improves 3 times of the switching traffics of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 9% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 88 ℃, mass concentration, loads 100V, 200mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 500 ℃ of following heat treatment 5min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Claims (1)
1. method that improves the low voltage anode aluminum foil specific volume is characterized in that:
1) electrochemical pre-treatment: it is 15～20% ammonium adipate solution that corrosive aluminum foil is placed 40～60 ℃, mass concentration, loads 2～5V, 10～300mA/cm
2Voltage and current carry out anodic oxidation, load time 40～80S improves 1～3 times of the switching traffic of ammonium adipate solution simultaneously;
2) formation of anode aluminium foil: it is 5～10% ammonium adipate solution that the aluminium foil after the electrochemical pre-treatment is placed 80～90 ℃, mass concentration, loads 10-100V, 200～1000mA/cm
2Voltage and current carry out continuous anodic oxidation, until forming anode aluminium foil;
3) heat treatment: the anode aluminium foil after will forming is at 500～600 ℃ of following heat treatment 2～5min;
4) mend to form: with the aluminium foil after the heat treatment once more in step 2) condition under carry out the anode aluminium foil that anodic oxidation obtains final high specific volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010926 CN102543478B (en) | 2012-01-13 | 2012-01-13 | Method for improving specific volume of low voltage aluminum anode foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010926 CN102543478B (en) | 2012-01-13 | 2012-01-13 | Method for improving specific volume of low voltage aluminum anode foil |
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| Publication Number | Publication Date |
|---|---|
| CN102543478A true CN102543478A (en) | 2012-07-04 |
| CN102543478B CN102543478B (en) | 2013-11-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210010926 Expired - Fee Related CN102543478B (en) | 2012-01-13 | 2012-01-13 | Method for improving specific volume of low voltage aluminum anode foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102543478B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624757A (en) * | 2016-03-18 | 2016-06-01 | 西安交通大学 | Industrial-frequency alternating-current anodic oxidation method of anode aluminum foil for aluminum electrolytic capacitor |
| CN105803505A (en) * | 2016-03-18 | 2016-07-27 | 西安交通大学 | Variable-frequency alternating-current anodic oxidation method for anode aluminum foil for aluminium electrolytic capacitor |
| CN106065488A (en) * | 2016-05-19 | 2016-11-02 | 西安交通大学 | A kind of method utilizing positive negative pulse stuffing anodizing to prepare anode aluminium foil |
Citations (7)
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|---|---|---|---|---|
| JPH0324714A (en) * | 1989-06-22 | 1991-02-01 | Showa Alum Corp | Etching neuclei forming method of aluminum foil for electrolytic capacitor electrode |
| JPH0653084A (en) * | 1992-07-30 | 1994-02-25 | Matsushita Electric Ind Co Ltd | Manufacture of electrode foil for aluminum electrolytic capacitor |
| CN1366095A (en) * | 2001-01-19 | 2002-08-28 | 江苏中联科技集团有限公司 | Three-stage process for preparing electrode foil used for low-voltage aluminium-electrolytic capacitor |
| CN1438662A (en) * | 2003-03-05 | 2003-08-27 | 西安交通大学 | Technology for preparing ande foil of aluminium electrolytic capacitor |
| CN101425378A (en) * | 2008-07-24 | 2009-05-06 | 东莞市东阳光电容器有限公司 | Mixed production method for electrolytic capacitor fine aluminum cathode foil corrosion and anodic oxidation |
| JP4641486B2 (en) * | 2005-10-28 | 2011-03-02 | ニチコン株式会社 | Method and apparatus for producing aluminum electrode foil for electrolytic capacitor |
| CN102212861A (en) * | 2011-04-21 | 2011-10-12 | 日丰（清远）电子有限公司 | Electrolyte for melting aluminum foil of anode of capacitor and aluminum foil melting method |
-
2012
- 2012-01-13 CN CN 201210010926 patent/CN102543478B/en not_active Expired - Fee Related
Patent Citations (7)
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|---|---|---|---|---|
| JPH0324714A (en) * | 1989-06-22 | 1991-02-01 | Showa Alum Corp | Etching neuclei forming method of aluminum foil for electrolytic capacitor electrode |
| JPH0653084A (en) * | 1992-07-30 | 1994-02-25 | Matsushita Electric Ind Co Ltd | Manufacture of electrode foil for aluminum electrolytic capacitor |
| CN1366095A (en) * | 2001-01-19 | 2002-08-28 | 江苏中联科技集团有限公司 | Three-stage process for preparing electrode foil used for low-voltage aluminium-electrolytic capacitor |
| CN1438662A (en) * | 2003-03-05 | 2003-08-27 | 西安交通大学 | Technology for preparing ande foil of aluminium electrolytic capacitor |
| JP4641486B2 (en) * | 2005-10-28 | 2011-03-02 | ニチコン株式会社 | Method and apparatus for producing aluminum electrode foil for electrolytic capacitor |
| CN101425378A (en) * | 2008-07-24 | 2009-05-06 | 东莞市东阳光电容器有限公司 | Mixed production method for electrolytic capacitor fine aluminum cathode foil corrosion and anodic oxidation |
| CN102212861A (en) * | 2011-04-21 | 2011-10-12 | 日丰（清远）电子有限公司 | Electrolyte for melting aluminum foil of anode of capacitor and aluminum foil melting method |
Non-Patent Citations (3)
| Title |
|---|
| 《thin soild film》 20080418 Xianfeng Du等 Formation of Al2O3-BaTiO3 composite thin film to increase the specific capacitance of aluminum electrolytic capacitor , * |
| XIANFENG DU等: "Formation of Al2O3–BaTiO3 composite thin film to increase the specific capacitance of aluminum electrolytic capacitor", 《THIN SOILD FILM》 * |
| 杨培霞等: "预处理工艺对制备多孔阳极氧化铝膜的影响", 《材料工程》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624757A (en) * | 2016-03-18 | 2016-06-01 | 西安交通大学 | Industrial-frequency alternating-current anodic oxidation method of anode aluminum foil for aluminum electrolytic capacitor |
| CN105803505A (en) * | 2016-03-18 | 2016-07-27 | 西安交通大学 | Variable-frequency alternating-current anodic oxidation method for anode aluminum foil for aluminium electrolytic capacitor |
| CN105803505B (en) * | 2016-03-18 | 2018-01-05 | 西安交通大学 | A kind of frequency-changing AC anodizing of aluminium electrolutic capacitor anode aluminium foil |
| CN105624757B (en) * | 2016-03-18 | 2018-01-05 | 西安交通大学 | A kind of industrial frequency AC anodizing of aluminium electrolutic capacitor anode aluminium foil |
| CN106065488A (en) * | 2016-05-19 | 2016-11-02 | 西安交通大学 | A kind of method utilizing positive negative pulse stuffing anodizing to prepare anode aluminium foil |
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| CN102543478B (en) | 2013-11-06 |
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Granted publication date: 20131106 |